Calcium-based catalyst system

ABSTRACT

The process and catalyst system of this invention can be utilized to synthesize a highly random styrene-butadiene rubber having a high trans content by solution polymerization. The styrene-butadiene rubber made by the process of this invention can be utilized in tire tread rubbers that exhibit improved wear characteristics. This invention more specifically reveals a catalyst system for use in isothermal polymerizations which consists essentially of (a) an organolithium compound, (b) a calcium alkoxide and (c) a lithium alkoxide. The subject invention further discloses a process for synthesizing a random styrene-butadiene rubber having a low vinyl content by a process which comprises copolymerizing styrene and 1,3-butadiene under isothermal conditions in an organic solvent in the presence of a catalyst system which consists essentially of (a) an organolithium compound, (b) a calcium alkoxide and (c) a lithium alkoxide. An amine can also be added to the catalyst system to increase the molecular weight (Mooney viscosity) of the rubber.

This application claims the benefit of U.S. Provisional Application No.60/102,706 filed Oct. 1, 1998.

BACKGROUND OF THE INVENTION

It is highly desirable for pneumatic tires to have good wet skidresistance, low rolling resistance and good wear characteristics. It hastraditionally been very difficult to improve the wear characteristics ofa tire without sacrificing its wet skid resistance and tractioncharacteristics. These properties depend, to a great extent, on thedynamic viscoelastic properties of the rubbers utilized in making thetire.

In order to reduce the rolling resistance and to improve the treadwearcharacteristics of tires, rubbers having a high rebound havetraditionally been utilized in making tire tread rubber compounds. Onthe other hand, in order to increase the wet skid resistance of a tire,rubbers which undergo a large energy loss have generally been utilizedin the tire's tread. In order to balance these two viscoelasticallyinconsistent properties, mixtures of various types of synthetic andnatural rubber are normally utilized in tire treads. For instance,various mixtures of styrene-butadiene rubber and polybutadiene rubberare commonly used as a rubbery material for automobile tire treads.

It is conventionally believed to be desirable for styrene-butadienerubber which is utilized in tire tread compounds to have a high level ofvinyl content (1,2-microstructure). It is also generally desirable forthe repeat units which are derived from styrene to be randomlydistributed throughout the polymer chains of the rubber. To achievethese objectives, styrene-butadiene rubbers are often synthesized bysolution polymerization which is conducted in the presence of one ormore modifying agents. Such modifying agents are well known in the artand are generally ethers, tertiary amines, chelating ethers or chelatingamines. Tetrahydrofuran, tetramethylethylene diamine (TMEDA) and diethylether are some representative examples of modifying agents which arecommonly utilized.

U.S. Pat. No. 5,284,927 discloses a process for preparing a rubberyterpolymer of styrene, isoprene and butadiene having multiple glasstransition temperatures and having an excellent combination ofproperties for use in making tire treads which comprises terpolymerizingstyrene, isoprene and 1,3-butadiene in an organic solvent at atemperature of no more than about 40° C. in the presence of (a)tripiperidino phosphine oxide, (b) an alkali metal alkoxide and (c) anorganolithium compound.

U.S. Pat. No. 5,534,592 discloses a process for preparing high vinylpolybutadiene rubber which comprises polymerizing 1,3-butadiene monomerwith a lithium initiator at a temperature which is within the range ofabout 5° C. to about 100° C. in the presence of a sodium alkoxide and apolar modifier, wherein the molar ratio of the sodium alkoxide to thepolar modifier is within the range of about 0.1:1 to about 10:1; andwherein the molar ratio of the sodium alkoxide to the lithium initiatoris within the range of about 0.01:1 to about 20:1.

U.S. Pat. No. 5,100,965 discloses a process for synthesizing a hightrans polymer which comprises adding (a) at least one organolithiuminitiator, (b) an organoaluminum compound, (c) a barium alkoxide and (d)a lithium alkoxide to a polymerization medium which is comprised of anorganic solvent and at least one conjugated diene monomer.

U.S. Pat. No. 5,100,965 further discloses that high trans polymers canbe utilized to improve, the characteristics of tire tread rubbercompounds. By utilizing high trans polymers in tire tread rubbercompounds, tires having improved wear characteristics, tear resistanceand low temperature performance can be made. Such high trans polymersinclude, trans-1,4-polybutadiene, trans styrene-isoprene-butadieneterpolymers, isoprene-butadiene copolymers and transstyrene-butadienecopolymers.

U.S. patent application Ser. No. 09/072,492, filed on May 4, 1998, U.S.Pat. No. 6,103,842 discloses a process for synthesizing a randomstyrene-butadiene rubber having a high trans content by a process whichcomprises copolymerizing styrene and 1,3-butadiene under isothermalconditions in an organic solvent in the presence of a catalyst systemwhich consists essentially of (a) an organolithium compound, (b) abarium alkoxide and (c) a lithium alkoxide.

SUMMARY OF THE INVENTION

This invention is based upon the unexpected discovery that a catalystsystem which consists of (a) an organometallic compound of a metalselected from the group consisting of lithium, potassium, magnesium,sodium, aluminum, zinc and tin, (b) a calcium compound and (c) a lithiumalkoxide, will catalyze the copolymerization of 1,3-butadiene monomerand styrene monomer into a styrene-butadiene copolymer having a randomdistribution of repeat units which are derived from styrene.Styrene-butadiene rubber made utilizing the catalyst system andtechniques of this invention is highly useful in the preparation of tiretread rubber compounds which exhibit improved wear characteristics.

It is preferred for the organometallic compound to be a lithium,potassium, magnesium or sodium compound. Organolithium compounds arenormally most preferred. The calcium compound will typically be acalcium carboxylate, a calcium phenolate, a calcium amine, a calciumamide, a calcium halide, a calcium nitrate, a calcium sulfate, a calciumphosphate or a calcium alcoholate. It is preferred for the calciumcompound to be soluble in the organic solvent used as the polymerizationmedium. It is accordingly preferred for the calcium compound to be acalcium alcoholate, a calcium carboxylate or a calcium phenolate. It istypically most preferred for the calcium compound to be a calciumalcoholate (a calcium alkoxide).

Calcium compounds, which are insoluble in the organic solvent used asthe polymerization medium, can also be utilized. However, such calciumcompounds will typically be preformed by mixing them with the othercatalyst components in the presence of a conjugated diene monomer, suchas 1,3-butadiene or isoprene.

The polymerizations of this invention are normally conducted in theabsence of organoaluminum compounds. A highly preferred catalyst systemfor the copolymerization of 1,3-butadiene monomer and styrene monomerconsists essentially of (a) an organolithium compound, (b) a calciumalkoxide and (c) a lithium alkoxide. The present invention accordinglyspecifically discloses a catalyst system which consists essentially of(a) an organolithium compound, (b) a calcium alkoxide and (c) a lithiumalkoxide.

The subject invention further discloses a process for synthesizing arandom styrene-butadiene rubber having a high trans content by a processwhich comprises copolymerizing styrene and 1,3-butadiene underisothermal conditions in an organic solvent in the presence of acatalyst system which consists essentially of (a) an organolithiumcompound, (b) a calcium alkoxide and (c) a lithium alkoxide.

The subject invention also reveals a process for synthesizing transpolybutadiene rubber having a vinyl content which is within the range ofabout 5 percent to about 15 percent by a process which comprisespolymerizing 1,3-butadiene in an organic solvent in the presence of acatalyst system which consists essentially of (a) an organolithiumcompound, (b) a calcium alkoxide and (c) a lithium alkoxide.

The present invention further reveals a catalyst system which consistsessentially of (a) an organometallic compound of a metal selected fromthe group consisting of lithium, potassium, magnesium, sodium, aluminum,zinc and tin, (b) a calcium compound and (c) a lithium alkoxide.

The subject invention further reveals a styrene-butadiene rubber whichis particularly useful in tire tread compounds, said styrene-butadienerubber being comprised of repeat units which are derived from about 3weight percent to about 50 weight percent styrene and from about 50weight percent to about 97 weight percent butadiene, wherein at least 98percent of the repeat units derived from styrene are in blockscontaining less than 5 repeat units, wherein at least 40 percent of therepeat units derived from styrene are in blocks containing only 1 repeatstyrene unit, wherein said rubber has a trans content which is withinthe range of 50 percent to 80 percent, wherein the rubber has a ciscontent which is within the range of 10 percent to 45 percent, whereinthe rubber has a vinyl content which is within the range of 5 percent to20 percent and wherein there are no segments of at least 100 repeatunits within the rubber which have a styrene content which differs fromthe total styrene content of the rubber by more than 10 percent.

DETAILED DESCRIPTION OF THE INVENTION

The polymerizations of the present invention will normally be carriedout in a hydrocarbon solvent which can be one or more aromatic,paraffinic or cycloparaffinic compounds. These solvents will normallycontain from 4 to 10 carbon atoms per molecule and will be liquid underthe conditions of the polymerization. Some representative examples ofsuitable organic solvents include pentane, isooctane, cyclohexane,methylcyclohexane, isohexane, n-heptane, n-octane, n-hexane, benzene,toluene, xylene, ethylbenzene, diethylbenzene, isobutylbenzene,petroleum ether, kerosene, petroleum spirits, petroleum naphtha and thelike, alone or in admixture.

In the solution polymerizations of this invention, there will normallybe from 5 to 30 weight percent monomers in the polymerization medium.Such polymerization media are, of course, comprised of the organicsolvent and monomers. In most cases, it will be preferred for thepolymerization medium to contain from 10 to 25 weight percent monomers.It is generally more preferred for the polymerization medium to contain15 to 20 weight percent monomers.

The solution styrene-butadiene rubbers made utilizing the catalystsystem and technique of this invention are comprised of repeat unitswhich are derived from 1,3-butadiene and styrene. Thesestyrene-butadiene rubbers will typically contain from about 5 weightpercent to about 50 weight percent styrene and from about 50 weightpercent to about 95 weight percent 1,3-butadiene. However, in somecases, the amount of styrene included will be as low as about 3 weightpercent. The styrene-butadiene rubber will more typically contain fromabout 10 weight percent to about 30 weight percent styrene and fromabout 70 weight percent to about 90 weight percent 1,3-butadiene. Thestyrene-butadiene rubber will preferably contain from about 15 weightpercent to about 25 weight percent styrene and from about 75 weightpercent to about 85 weight percent 1,3-butadiene. Thesestyrene-butadiene rubbers typically have a melting point which is withinthe range of about −10° C. to about −20° C.

Styrene-butadiene copolymer resins containing from about 50 weightpercent to about 95 weight percent styrene and from about 5 weightpercent to about 50 weight percent 1,3-butadiene can also be synthesizedutilizing the catalyst systems of this invention. Such copolymers havingglass transition temperatures within the range of 7° C. to 70° C. can beused as toner resins.

In the styrene-butadiene rubbers of this invention, the distribution ofrepeat units derived from styrene and butadiene is essentially random.The term “random” as used herein means that less than 5 percent of thetotal quantity of repeat units derived from styrene are in blockscontaining five or more styrene repeat units. In other words, more than95 percent of the repeat units derived from styrene are in blockscontaining less than five repeat units. A large quantity of repeat unitsderived from styrene will be in blocks containing only one styrenerepeat unit. Such blocks containing one styrene repeat unit are bound onboth sides by repeat units which are derived from 1,3-butadiene.

In styrene-butadiene rubbers containing less than about 30 weightpercent bound styrene which are made with the catalyst system of thisinvention, less than 2 percent of the total quantity of repeat unitsderived from styrene are in blocks containing five or more styrenerepeat units. In other words, more than 98 percent of the repeat unitsderived from styrene are in blocks containing less than five repeatunits. In such styrene-butadiene rubbers, over 40 percent of repeatunits derived from styrene will be in blocks containing only one styrenerepeat unit, over 75 percent of the repeat units derived from styrenewill be in blocks containing less than 3 repeat units and over 90percent of the repeat units derived from styrene will be in blockscontaining less than 4 repeat units.

In styrene-butadiene rubbers containing less than about 20 weightpercent bound styrene which are made with the catalyst system of thisinvention, less than 1 percent of the total quantity of repeat unitsderived from styrene are in blocks containing 4 or more styrene repeatunits. In other words, more than 99 percent of the repeat units derivedfrom styrene are in blocks containing less than 4 repeat units. In suchstyrene-butadiene rubbers, over 60 percent of repeat units derived fromstyrene will be in blocks containing only one styrene repeat unit-andover 90 percent of the repeat units derived from styrene will be inblocks containing less than 3 repeat units.

The styrene-butadiene copolymers of this invention also have aconsistent composition throughout their polymer chains. In other words,the styrene content of the polymer will be the same from the beginningto the end of the polymer chain. No segments of at least 100 repeatunits within the polymer will have a styrene content which differs fromthe total styrene content of the polymer by more than 10 percent. Suchstyrene-butadiene copolymers will typically contain no segments having alength of at least 100 repeat units which have a styrene content whichdiffers from the total styrene content of the polymer by more than about5 percent.

The polymerizations of this invention are initiated by adding (a) anorganometallic compound of a metal selected from the group consisting oflithium, potassium, magnesium, sodium, aluminum, zinc and tin, (b) acalcium compound and (c) a lithium alkoxide to a polymerization mediumcontaining the monomers to be polymerized. The polymerizations of thisinvention are typically initiated by adding an organolithium compound, acalcium alkoxide and a lithium alkoxide to a polymerization mediumcontaining the styrene and 1,3-butadiene monomers. Such polymerizationcan be carried out utilizing batch, semi-continuous or continuoustechniques.

The organolithium compounds which can be employed in the process of thisinvention include the monofunctional and multifunctional initiator typesknown for polymerizing the conjugated diolefin monomers. Themultifunctional organolithium initiators can be either specificorganolithium compounds or can be multifunctional types which are notnecessarily specific compounds but rather represent reproduciblecompositions of regulable functionality.

The choice of initiator can be governed by the degree of branching andthe degree of elasticity desired for the polymer, the nature of thefeedstock and the like. With regard to the feedstock employed as thesource of conjugated diene, for example, the multifunctional initiatortypes generally are preferred when a low concentration diene stream isat least a portion of the feedstock, since some components present inthe unpurified low concentration diene stream may tend to react withcarbon lithium bonds to deactivate the activity of the organolithiumcompound, thus necessitating the presence of sufficient lithiumfunctionality so as to override such effects.

The multifunctional organolithium compounds which can be used includethose prepared by reacting an organomonolithium compounded with amultivinylphosphine or with a multivinylsilane, such a reactionpreferably being conducted in an inert diluent such as a hydrocarbon ora mixture of a hydrocarbon and a polar organic compound. The reactionbetween the multivinylsilane or multivinylphosphine and theorganomonolithium compound can result in a precipitate which can besolubilized, if desired, by adding a solubilizing monomer such as aconjugated diene or monovinyl aromatic compound, after reaction of theprimary components. Alternatively, the reaction can be conducted in thepresence of a minor amount of the solubilizing monomer. The relativeamounts of the organomonolithium compound and the multivinylsilane orthe multivinylphosphine preferably should be in the range of about 0.33to 4 moles of organomonolithium compound per mole of vinyl groupspresent in the multivinylsilane or multivinylphosphine employed. Itshould be noted that such multifunctional initiators are commonly usedas mixtures of compounds rather than as specific individual compounds.Exemplary organomonolithium compounds include ethyl lithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-octyl lithium, n-eicosyllithium, phenyl lithium, 2-naphthyllithium, 4-butylphenyllithium,4-tolyllithium, 4-phenylbutyllithium, cyclohexyl lithium and the like.

Exemplary multivinylsilane compounds include tetravinylsilane,methyltrivinylsilane, diethyldivinylsilane, di-n-dodecyldivinylsilane,cyclohexyltrivinylsilane, phenyltrivinylsilane, benzyltrivinylsilane,(3-ethylcyclohexyl) (3-n-butylphenyl)divinylsilane and the like.

Exemplary multivinylphosphine compounds include trivinylphosphine,methyldivinylphosphine, dodecyldivinylphosphine, phenyldivinylphosphine,cyclooctyldivinylphosphine and the like.

Other multifunctional polymerization initiators can be prepared byutilizing an organomonolithium compound, further together with amultivinylaromatic compound and either a conjugated diene ormonovinylaromatic compound or both. These ingredients can be chargedinitially, usually in the presence of a hydrocarbon or a mixture of ahydrocarbon and a polar organic compound as a diluent. Alternatively, amultifunctional polymerization initiator can be prepared in a two-stepprocess by reacting the organomonolithium compound with a conjugateddiene or monovinyl aromatic compound additive and then adding themultivinyl aromatic compound. Any of the conjugated dienes or monovinylaromatic compounds described can be employed. The ratio of conjugateddiene or monovinyl aromatic compound additive employed preferably shouldbe in the range of about 2 to 15 moles of polymerizable compound permole of organolithium compound. The amount of multivinylaromaticcompound employed preferably should be in the range of about 0.05 to 2moles per mole of organomonolithium compound.

Exemplary multivinyl aromatic compounds include 1,2-divinylbenzene,1,3-divinylbenzene, 1,4-divinylbenzene, 1,2,4-trivinylbenzene,1,3-divinylnaphthalene, 1,8-divinylnaphthalene,1,3,5-trivinylnaphthalene, 2,4-divinylbiphenyl, 3,5,4′-trivinylbiphenyl,m-diisopropenyl benzene, p-diisopropenyl benzene,1,3-divinyl-4,5,8-tributylnaphthalene and the like. Divinyl aromatichydrocarbons containing up to 18 carbon atoms per molecule arepreferred, particularly divinylbenzene as either the ortho, meta or paraisomer, and commercial divinylbenzene, which is a mixture of the threeisomers, and other compounds such as the ethyl styrenes, also is quitesatisfactory.

Other types of multifunctional lithium compounds can be employed such asthose prepared by contacting a sec- or tert-organomonolithium compoundwith 1,3-butadiene, at a ratio of about 2 to 4 moles of theorganomonolithium compound per mole of the 1,3-butadiene, in the absenceof added polar material in this instance, with the contacting preferablybeing conducted in an inert hydrocarbon diluent, though contactingwithout the diluent can be employed, if desired.

Alternatively, specific organolithium compounds can be employed asinitiators, if desired, in the preparation of polymers in accordancewith the present invention. These can be represented by R(Li)x wherein Rrepresents a hydrocarbyl radical containing from 1 to 20 carbon atoms,and wherein x is an integer of 1 to 4. Exemplary organolithium compoundsare methyl lithium, isopropyl lithium, n-butyllithium, sec-butyllithium,tert-octyl lithium, n-decyl lithium, phenyl lithium, 1-naphthyllithium,4-butylphenyllithium, p-tolyl lithium, 4-phenylbutyllithium, cyclohexyllithium, 4-butylcyclohexyllithium, 4-cyclohexylbutyllithium,dilithiomethane, 1,4-dilithiobutane, 1,10-dilithiodecane,1,20-dilithioeicosane, 1,4-dilithiocyclohexane, 1,4-dilithio-2-butane,1,8-dilithio-3-decene, 1,2-dilithio-1,8-diphenyloctane,1,4-dilithiobenzene, 1,4-dilithionaphthalene, 9,10-dilithioanthracene,1,2-dilithio-1,2-diphenylethane, 1,3,5-trilithiopentane,1,5,15-trilithioeicosane, 1,3,5-trilithiocyclohexane,1,3,5,8-tetralithiodecane, 1,5,10,20-tetralithioeicosane,1,2,4,6-tetralithiocyclohexane, 4,4′-dilithiobiphenyl and the like.

The calcium alkoxides which can be utilized typically have thestructural formula:

R¹—O—Ca—O—R²

wherein R¹ and R² can be the same or different and represent alkylgroups (including cycloalkyl groups), aryl groups, alkaryl groups orarylalkyl groups. Some representative examples of suitable calciumalkoxides include calcium dimethoxide, calcium diethoxide, calciumdiisopropoxide, calcium di-n-butoxide, calcium di-sec-butoxide, calciumdi-t-butoxide, calcium di(1,1-dimethylpropoxide), calciumdi(1,2-dimethylpropoxide), calcium di(1,1-dimethylbutoxide), calciumdi(1,10-dimethylpentoxide), calcium di(2-ethylhexanoxide), calciumdi(1-methylheptoxide), calcium diphenoxide, calciumdi(p-methylphenoxide), calcium di(p-octylphenoxide), calciumdi(p-nonylphenoxide), calcium di(p-dodecylphenoxide), calciumdi(α-naphthoxide), calcium di(β-naphthoxide), calcium(o-methoxyphenoxide), calcium (o-methoxyphenoxide), calciumdi(m-methoxyphenoxide), calcium di(p-methoxyphenoxide), calcium(o-ethoxyphenoxide), calcium (4-methoxy-1-naphthoxide) and the like.Cyclic compounds, such as calcium ditetrahydrofurfurylate, can also beutilized in the catalyst system.

Calcium alkoxides can be prepared using inexpensive starting materialsusing a relatively simple procedure. This is done by reacting calciumhydroxide, Ca(OH)₂, with an alcohol of the formula ROH at a temperaturewhich is within the range of about 150° C. to about 250° C. Thisreaction can be depicted as follows:

Ca(OH)₂+2ROH→Ca(OR)₂+2H₂O

wherein R represents an alkyl group, an aryl group or an alkaryl group.R will preferably be a 2-ethylhexyl group, a nonylphenyl group, adodecylphenyl group, a tetrahydrofurfuryl group or a furfuryl group.This reaction will preferably be conducted at a temperature which iswithin the range of about 175° C. to 200° C. with the alcohol acting asthe solvent for the reaction. The reaction will normally be carried outat a temperature which is above the boiling point of the alcohol for aperiod of 2-3 hours. After the reaction has been completed, excessalcohol is removed by distillation under vacuum or evaporation. Then,the calcium alkoxide is recovered by dissolving it in a suitable organicsolvent; such as, ethyl benzene, toluene or xylene.

The lithium alkoxide compounds which can be utilized have the structuralformula:

LiOR

wherein R represents an alkyl group, an aryl group, an alkaryl group, anarylalkyl group or a hydrocarbon group containing at least one heteroatom selected from the group consisting of oxygen atoms and nitrogenatoms. The lithium alkoxide can be synthesized by reacting anorganolithium compound, metallic lithium or lithium hydride with analcohol. The organolithium compound, metallic or lithium hydride can bereacted with the alcohol at a molar ratio of 0.5:1 to 3:2. It ispreferred for the alcohol to be reacted with an equal molar amount ofthe organolithium compound, metallic lithium or lithium hydride. Somerepresentative examples of alcohols which can be utilized in preparingthe lithium alkoxide include methanol, ethanol, n-propyl alcohol,isopropyl alcohol, t-butanol, sec-butanol, cyclohexanol, octanol,2-ethylhexanol, p-cresol, m-cresol, nonyl phenol, hexylphenol,tetrahydrofuryl alcohol, furfuryl alcohol, 3-methyltetrahydrofurfurylalcohol, oligomer of tetrahydrofurfuryl alcohol, ethylene glycolmonophenyl ether, ethylene glycol monobutyl ether,N,N-dimethylethanolamine, N,N-diethylethanolamine,N,N-dibutylethanolamine, N,N-diphenylethanolamine,N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine,N-phenyldiethanolamine, N,N-dimethylpropanolamine,N,N-dibutylpropanolamine, N-methyldipropanolamine,N-ethyldipropanolamine, 1-(2-hydroxyethyl)pyrrolidine,2-methyl-1-(2-hydroxyethyl)pyrrolidine, 1-piperidineethanol,2-phenyl-1-piperidineethanol, 2-ethyl-1-piperidinepropanol,N-β-hydroxyethylmorpholine, 2-ethyl-N-8-hydroxyethylmorpholine,1-piperazineethanol, 1-piperazinepropanol,N,N′bis(β-hydroxyethyl)piperazine, N,N′-bis(Y-hydroxypropyl)-piperazine,2-(β-hydroxyethyl)pyridine, 2-(γ-hydroxypropyl)pyridine and the like.

The molar ratio of the lithium alkoxide to the calcium alkoxide will bewithin the range of about 1:1 to about 20:1 and will preferably bewithin the range of 5:2 to 10:1. The molar ratio of the lithium alkoxideto the calcium alkoxide will most preferably be within the range ofabout 3:1 to about 5:1. The molar ratio of the alkyl lithium compound tothe calcium alkoxide will be within the range of about 1:1 to about 6:1and will preferably be within the range of 3:2 to 4:1. The molar ratioof the alkyl lithium compound to the calcium alkoxide will mostpreferably be within the range of 2:1 to 3:1.

The organolithium compound will normally be present in thepolymerization medium in an amount which is within the range of about0.01 to 1 phm (parts by 100 parts by weight of monomer). In most cases,from 0.01 phm to 0.1 phm of the organolithium compound will be utilizedwith it being preferred to utilize from 0.025 phm to 0.07 phm of theorganolithium compound in the polymerization medium.

The polymerization temperature utilized can vary over a broadtemperature range of from about 20° C. to about 180° C. In most cases, atemperature within the range of about 40° C. to about 120° C. will beutilized. It is typically most preferred for the polymerizationtemperature to be within the range of about 70° C. to about 100° C. Thepressure used will normally be sufficient to maintain a substantiallyliquid phase under the conditions of the polymerization reaction.

Polar modifiers can be used to modify the microstructure of the rubberypolymer being synthesized. Ethers and amines which act as Lewis basesare representative examples of polar modifiers that can be utilized.Some specific examples of typical polar modifiers include diethyl ether,di-n-propyl ether, diisopropyl ether, di-n-butyl ether, tetrahydrofuran,dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether,diethylene glycol dimethyl ether, diethylene glycol diethyl ether,triethylene glycol dimethyl ether, trimethylamine, triethylamine,N,N,N′,N′-tetramethylethylenediamine (TMEDA), N-methyl morpholine,N-ethyl morpholine, N-phenyl morpholine and the like.Dipiperidinoethane, dipyrrolidinoethane, tetramethylethylene diamine,diethylene glycol, dimethyl ether, TMEDA, tetrahydrofuran, piperidine,pyridine and hexamethylimine are representative of highly preferredmodifiers. U.S. Pat. No. 4,022,959 describes the use of ethers andtertiary amines as polar modifiers in greater detail.

The polymerization is conducted for a length of time sufficient topermit substantially complete polymerization of monomers. In otherwords, the polymerization is normally carried out until high conversionsare attained. The polymerization can then be terminated using a standardtechnique. The polymerization can be terminated with a conventionalnoncoupling type of terminator (such as, water, an acid and a loweralcohol) or with a coupling agent.

Coupling agents can be used in order to improve the cold flowcharacteristics of the rubber and rolling resistance of tires madetherefrom. It also leads to better processability and other beneficialproperties. A wide variety of compounds suitable for such purposes canbe employed. Some representative examples of suitable coupling agentsinclude: multivinylaromatic compounds, multiepoxides, multiisocyanates,multiimines, multialdehydes, multiketones, multihalides,multianhydrides, multiesters which are the esters of polyalcohols withmonocarboxylic acids, and the diesters which are esters of monohydricalcohols with dicarboxylic acids and the like.

Examples of suitable multivinylaromatic compounds includedivinylbenzene, 1,2,4-trivinylbenzene, 1,3-divinylnaphthalene,1,8-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4-divinylbiphenyland the like. The divinylaromatic hydrocarbons are preferred,particularly divinylbenzene in either its ortho, meta or para isomer.Commercial divinylbenzene which is a mixture of the three isomers andother compounds is quite satisfactory.

While any multiepoxide can be used, liquids are preferred since they aremore readily handled and form a relatively small nucleus for the radialpolymer. Especially preferred among the multiepoxides are the epoxidizedhydrocarbon polymers such as epoxidized liquid polybutadienes and theepoxidized vegetable oils such as epoxidized soybean oil and epoxidizedlinseed oil. Other epoxy compounds, such as 1,2,5,6,9,10-triepoxydecane,also can be used.

Examples of suitable multiisocyanates includebenzene-1,2,4-triisocyanate, naphthalene-1,2,5,7-tetraisocyanate and thelike. Especially suitable is a commercially available product known asPAPI-1, a polyarylpolyisocyanate having an average of three isocyanategroups per molecule and an average molecular weight of about 380. Such acompound can be visualized as a series of isocyanate-substituted benzenerings joined through methylene linkages.

The multiimines, which are also known as multiaziridinyl compounds,preferably are those containing three or more aziridine rings permolecule. Examples of such compounds include the triaziridinyl phosphineoxides or sulfides such as tri(1-ariridinyl)phosphine oxide,tri(2-methyl-1-ariridinyl)phosphine oxide,tri(2-ethyl-3-decyl-1-ariridinyl)phosphine sulfide and the like.

The multialdehydes are represented by compounds such as1,4,7-naphthalene tricarboxyaldehyde, 1,7,9-anthracenetricarboxyaldehyde, 1,1,5-pentane tricarboxyaldehyde and similarmultialdehyde containing aliphatic and aromatic compounds. Themultiketones can be represented by compounds such as1,4,9,10-anthraceneterone, 2,3-diacetonylcyclohexanone and the like.Examples of the multianhydrides include pyromellitic dianhydride,styrene-maleic anhydride copolymers and the like. Examples of themultiesters include diethyladipate, triethyl citrate,1,3,5-tricarbethoxybenzene and the like.

The preferred multihalides are silicon tetrahalides (such as silicontetrachloride, silicon tetrabromide and silicon tetraiodide) and thetrihalosilanes (such as trifluorosilane, trichlorosilane,trichloroethylsilane, tribromobenzylsilane and the like). Also preferredare the multihalogen-substituted hydrocarbons (such as,1,3,5-tri(bromomethyl)benzene and 2,4,6,9-tetrachloro-3,7-decadiene) inwhich the halogen is attached to a carbon atom which is alpha to anactivating group such as an ether linkage, a carbonyl group or acarbon-to-carbon double bond. Substituents inert with respect to lithiumatoms in the terminally reactive polymer can also be present in theactive halogen-containing compounds. Alternatively, other suitablereactive groups different from the halogen as described above can bepresent.

Examples of compounds containing more than one type of functional groupinclude 1,3-dichloro-2-propanone, 2,2-dibromo-3-decanone,3,5,5-trifluoro-4-octanone, 2,4-dibromo-3-pentanone,1,2,4,5-diepoxy-3-pentanone, 1,2,4,5-diepoxy-3-hexanone,1,2,11,12-diepoxy-8-pentadecanone, 1,3,18,19-diepoxy-7,14-eicosanedioneand the like.

In addition to the silicon multihalides as described hereinabove, othermetal multihalides, particularly those of tin, lead or germanium, alsocan be readily employed as coupling and branching agents. Difunctionalcounterparts of these agents also can be employed, whereby a linearpolymer rather than a branched polymer results. Monofunctionalcounterparts can be used to end cap the rubbery polymer. For instance,trialkyl tin chlorides, such as tri-isobutyl tin chloride, can beutilized to end cap the rubbery polymer.

Broadly, and exemplary, a range of about 0.01 to 4.5 milliequivalents ofcoupling agent are employed per 100 grams of monomer. It is preferred toutilize about 0.01 to about 1.5 milliequivalents of the coupling agentper 100 grams of monomer to obtain the desired Mooney viscosity. Thelarger quantities tend to result in production of polymers containingterminally reactive groups or insufficient coupling. One equivalent oftreating agent per equivalent of lithium is considered optimum amountfor maximum branching, if this result is desired in the production line.The coupling agent can be added in hydrocarbon solution (e.g., incyclohexane) to the polymerization admixture in the final reactor withsuitable mixing for distribution and reaction.

After the copolymerization has been completed, the styrene-butadieneelastomer can be recovered from the organic solvent. Thestyrene-butadiene rubber can be recovered from the organic solvent andresidue by means such as decantation, filtration, centrification and thelike. It is often desirable to precipitate the segmented polymer fromthe organic solvent by the addition of lower alcohols containing fromabout 1 to about 4 carbon atoms to the polymer solution. Suitable loweralcohols for precipitation of the segmented polymer from the polymercement include methanol, ethanol, isopropyl alcohol, normal-propylalcohol and t-butyl alcohol. The utilization of lower alcohols toprecipitate the rubber from the polymer cement also “kills” the livingpolymer by inactivating lithium end groups. After the segmented polymeris recovered from the solution, steam-stripping can be employed toreduce the level of volatile organic compounds in the rubber.

There are valuable benefits associated with utilizing thestyrene-butadiene rubbers of this invention in making tire treadcompounds. For instance, the styrene-butadiene rubber of this inventioncan be blended with natural rubber to make tread compounds for passengertires which exhibit outstanding rolling resistance, traction and treadwear characteristics. In-cases where tread wear is of great importance,high cis-1,4-polybutadiene can also be included in the blend. In anycase, the styrene-butadiene rubbers of this invention can be used toimprove the traction, tread wear and rolling resistance of tires madetherewith.

This invention is illustrated by the following examples which are merelyfor the purpose of illustration and are not to be regarded as limitingthe scope of the invention or the manner in which it can be practiced.Unless specifically indicated otherwise, parts and percentages are givenby weight.

EXAMPLES

The calcium-based catalyst of this invention can be used in thehomopolymerization of 1,3-butadiene into polybutadiene (PBD), in thehomopolymerization of isoprene into polyisoprene (PI), in thecopolymerization of styrene and 1,3-butadiene into styrene-butadienerubber (SBR) and in the terpolymerization of styrene, isoprene and1,3-butadiene into styrene-isoprene-butadiene rubber (SIBR). Thecalcium-based catalyst system of this invention can be prepared in-situor can be preformed.

Preparation of Solution SBR

A styrene/butadiene premix that contained 10 percent styrene and 90percent 1,3-butadiene was charged in a one-gallon (3.785 liter) reactorequipped with a mechanical stirrer and under a blanket of nitrogen. Heatwas applied to this reactor until the pre-mix temperature reached 75° C.At this point, catalyst was introduced. The catalyst included calciumtetrahydrofurfuryl alcohol (the calcium salt of tetrafydrofurfurylalcohol which is hexane-soluble) which was introduced at a level of 1mmole per 100 g of monomer. This was followed by the addition of 2 mmoleof n-butyl lithium and 2 mmole of lithium t-butoxide, based on 100 g ofmonomer. It should be noted that the catalyst can be preformed or thatthe catalyst components can be added individually. The samples weretaken at various time intervals and analyzed by gas chromatography (GC)analysis. The data showed that the 30/70 monomer composition in thepre-mix (monomer plus hexane) resulted in a copolymer having a constantcomposition of 30 percent styrene and 70 percent butadiene. Thus, arandom copolymer was made throughout the polymerization. A monomerconversion of approximately 90 percent was reached after only one hourof polymerization time. The polymer was analyzed and was determined tohave a glass transition temperature (Tg) of −54° C., a 20 percent bound1,2-polybutadiene (vinyl)content and random styrene sequences. Thispolymerization with the calcium-based catalyst system offers theadvantage of promoting a much faster rate of polymerization than can beattained utilizing barium based catalyst systems.

Variations in the present invention are possible in light of thedescription of it provided herein. While certain representativeembodiments and details have been shown for the purpose of illustratingthe subject invention, it will be apparent to those skilled in this artthat various changes and modifications can be made therein withoutdeparting from the scope of the subject invention. It is, therefore, tobe understood that changes can be made in the particular embodimentsdescribed which will be within the full intended scope of the inventionas defined by the following appended claims.

What is claimed is:
 1. A process for synthesizing a randomstyrene-butadiene rubber having a high trans, low vinyl content by aprocess which comprises copolymerizing styrene and 1,3-butadiene in anorganic solvent in the presence of a catalyst system which consistsessentially of (a) an organolithium compound, (b) a calcium alkoxide and(c) a lithium alkoxide.
 2. A process for synthesizing transpolybutadiene rubber having a vinyl content which is within the range ofabout 5 percent to about 20 percent by a process which comprisespolymerizing 1,3-butadiene in an organic solvent in the presence of acatalyst system which consists essentially of (a) an organolithiumcompound, (b) a calcium alkoxide and (c) a lithium alkoxide.
 3. Aprocess for the synthesis of a random styrene-butadiene rubber asspecified in claim 1 wherein from about 3 weight percent to about 50weight percent styrene is copolymerized with about 50 weight percent toabout 97 weight percent 1,3-butadiene.
 4. A process for the synthesis ofa random styrene-butadiene rubber as specified in claim 3 wherein saidcopolymerization is conducted at a temperature which is within the rangeof about 40° C. to about 120° C.
 5. A process for the synthesis of arandom styrene-butadiene rubber as specified in claim 4 wherein saidorganolithium compound is present in an amount which is within the rangeof about 0.01 phm to about 0.1 phm.
 6. A process for the synthesis of arandom styrene-butadiene rubber as specified in claim 5 wherein themolar ratio of the lithium alkoxide to the calcium alkoxide is withinthe range of about 2:1 to about 20:1; and wherein the molar ratio of thealkyl lithium compound to the calcium alkoxide is within the range ofabout 1:1 to about 6:1.
 7. A process for the synthesis of a randomstyrene-butadiene rubber as specified in claim 6 wherein the calciumalkoxide is selected from the group consisting of calcium dimethoxide,calcium diethoxide, calcium diisopropoxide, calcium di-n-butoxide,calcium di-sec-butoxide, calcium di-t-butoxide, calciumdi(1,1-dimethylpropoxide), calcium di(1,2-dimethyl-propoxide), calciumdi(1,1-dimethylbutoxide), calcium di(1,10-dimethylpentoxide), calciumdi(2-ethyl-hexanoxide), calcium di(1-methylheptoxide), calciumdiphenoxide, calcium di(p-methylphenoxide), calciumdi(p-octylphenoxide), calcium di(p-nonylphenoxide), calciumdi(p-dodecylphenoxide), calcium di(α-naphthoxide), calciumdi(β-naphthoxide), calcium (o-methoxyphenoxide), calcium(o-methoxyphenoxide), calcium di(m-methoxyphenoxide), calciumdi(p-methoxy-phenoxide), calcium (o-ethoxyphenoxide) and calcium(4-methoxy-1-naphthoxide); wherein the organolithium compound is anorganomonolithium compound; and wherein the lithium alkoxide is make byreacting an organolithium compound, metallic lithium or lithium hydridewith an alcohol selected from the group consisting of methanol, ethanol,n-propyl alcohol, isopropyl alcohol, t-butanol, sec-butanol,cyclohexanol, octanol, 2-ethylhexanol, p-cresol, m-cresol, nonyl phenol,hexylphenol, tetrahydrofuryl alcohol, furfuryl alcohol,3-tnethyltetrahydrofurfuryl alcohol, oligomer of tetrahydrofurfurylalcohol, ethylene glycol monophenyl ether, ethylene glycol monobutylether, N,N-dimethylethanolamine, N,N-diethylethanolamine,N,N-dibutylethanolamine, N,N-diphenylethanolamine,N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine,N-phenyldiethanolamine, N,N-dimethylpropanolamine,N,N-dibutylpropanolamine, N-methyldipropanolamine,N-ethyldipropanolamine, 1-(2-hydroxyethyl)pyrrolidine,2-methyl-1(2-hydroxyethyl)pyrrolidine, 1-piperidineethanol,2-phenyl-1-piperidineethanol, 2-ethyl-1-piperidinepropanol,N-β-hydroxyethylmorpholine, 2-ethyl-N-8-hydroxyethylmorpholine,1-piperazineethanol, 1-piperazinepropanol,N,N′bis(β-hydroxyethyl)piperazine, N,N′-bis(Y-hydroxypropyl)-piperazine,2-(β-hydroxyethyl)pyridine and 2-(γ-hydroxypropyl)pyridine.
 8. A processfor the synthesis of a random styrene-butadiene rubber as specified inclaim 7 wherein the molar ratio of the lithium alkoxide to the calciumalkoxide is within the range of about 5:2 to about 10:1, and wherein themolar ratio of the alkyl lithium compound to the calcium alkoxide iswithin the range of about 3:2 to about 4:1.
 9. A process for thesynthesis of a random styrene-butadiene rubber as specified in claimwherein 8 the molar ratio of the lithium alkoxide to the calciumalkoxide is within the range of about 3:1 to about 5:1; wherein themolar ratio of the alkyl lithium compound to the calcium alkoxide iswithin the range of about 2:1 to about 3:1; wherein from about 15 weightpercent to about 25 weight percent styrene is copolymerized with about75 weight percent to about 85 weight percent 1,3-butadiene; and whereinsaid copolymerization is conducted at a temperature which is within therange of about 60° C. to about 85°.
 10. A process for the synthesis of arandom styrene-butadiene resin having a glass transition temperaturewhich is within the range of about 7° C. to about 70° C. as specified inclaimed 1 wherein from about 50 weight percent to about 95 weightpercent styrene is copolymerized with about 5 weight percent to about 50weight percent 1,3-butadiene.
 11. A process as specified in claim 1which further comprises terpolymerizing isoprene with said 1,3-butadieneand said styrene.
 12. A process as specified in claim 1 which furthercomprises coupling the random styrene-butadiene rubber with tintetrachloride.
 13. A process as specified in claim 1 which furthercomprises coupling the random styrene-butadiene rubber with silicontetrachloride.
 14. A process as specified in claim 1 wherein saidprocess is conducted in the presence of a polar modifier.
 15. A processfor synthesizing a random isoprene-butadiene rubber having a high trans,low vinyl content which comprises copolymerizing isoprene and1,3-butadiene monomer in an organic solvent in the presence of acatalyst system which consists essentially of (a) an organolithiumcompound, (b) a calcium alkoxide and (c) a lithium alkoxide.